CN105051014A - Materials for electronic devices - Google Patents

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CN105051014A
CN105051014A CN201480017424.7A CN201480017424A CN105051014A CN 105051014 A CN105051014 A CN 105051014A CN 201480017424 A CN201480017424 A CN 201480017424A CN 105051014 A CN105051014 A CN 105051014A
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replaces
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CN105051014B (en
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菲利普·斯托塞尔
埃米尔·侯赛因·帕勒姆
克里斯托夫·普夫卢姆
安雅·雅提斯奇
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Merck Patent GmbH
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Merck Patent GmbH
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    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D279/18—[b, e]-condensed with two six-membered rings
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Indole Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

The present application relates to a compound of a formula (I) which comprises a benzene group that is substituted with a group selected from carbazole derivatives and bridged amines and with an electron attracting group, wherein the two groups are located in the ortho-position in reslation to one another. The present application further relates to the use of the compound of the formula (I) in an electronic device, and to a method of producing the compound of the formula (I).

Description

For the material of electron device
The application relates to formula (I) compound, and it has the phenyl group of the group replacement being selected from carbazole derivative and bridge joint amine and has electron-withdrawing group, and wherein said two kinds of groups are in ortho position each other.Described compound may be used in electron device.
Electron device in the present context is especially interpreted as referring to the electron device being called as organic electronic devices, and it contains organic semiconductor material as functional materials.Even more particularly, this is interpreted as other electron device of referring to organic electroluminescence device (OLED) and hereafter mentioning in detail in the specific embodiment of the present invention.
In general, term OLED is interpreted as referring to containing at least one organic materials and the electron device of the luminescence when applying voltage.The precise structure of OLED is especially described in US4539507, US5151629, EP0676461 and WO98/27136.
In electron device, especially OLED, for improvement performance data, especially, there is very large interest in life-span and efficiency and operating voltage.Organic luminophor layer, the emitter compound especially wherein existed, plays an important role.
In order to solve this technical problem, continue the novel material seeking the emitter compound be suitable as in luminescent layer, it especially combines with substrate material.
The substrate material comprised in the system of two or more materials is interpreted as referring to the component in the mixture with larger proportion.Correspondingly, the doping agent comprised in the system of two or more materials is interpreted as referring to the component had in the mixture compared with small proportion.
In the context of this application, the emitter compound of luminescent layer is the compound of the luminescence when electron device works.
In the luminescent layer of OLED, one or more dopant compound normally luminophor, and one or more matrix compounds are not luminous.Such as, such as, but also may have exception, the compound existed with small proportion in the mixture of luminescent layer is not regarded as doping agent according to above-mentioned definition, but luminous but meet other function, transferring charge.
Prior art comprises such as from the compound containing one or more carbazole group that WO2005/039246, US2005/0069729, JP2004/288381, EP1205527 or WO2008/086851 are known.Described compound is especially suitable as the compound of the substrate material of the luminescent layer of OLED or the electron transfer layer as OLED.
In addition, WO2012/143079 discloses on benzene 1, and 3,5 positions have the compound of three carbazole groups.Other substituting group is then selected from such as alkyl group.Described compound is especially suitable in the luminescent layer of OLED.
Other compound is disclosed in H.Uoyama etc., Nature (nature) 2012,492,234 and thereafter in page, these compounds contain multiple carbazole group and cyano group that is multiple and phenyl ring bonding, and wherein said carbazole group and described cyano group are relative to each other in the arrangement of restriction.In these compounds, always there is the carbazole group of at least two alignment therewith arrangements on phenyl ring.Described compound is used in the luminescent layer of OLED.
Although there are these results, but still need to be suitable in electron device, especially for the novel cpd in the luminescent layer of OLED.
Find now, surprisingly, the compound having at least one carbazole derivative being bonded to phenyl ring and have at least one electron-withdrawing group on its ortho position has extraordinary suitability for using in electron device, substituting group on wherein said phenyl ring is relative to each other in the arrangement of restriction, as shown in the formula defined in (I).More specifically, they are suitable as the emitter compound in luminescent layer particularly highlightedly.
OLED containing described compound has extraordinary power efficiency and very long life-span surprisingly.In addition, they preferably have low operating voltage.In addition, when being used as emitter compound, they can contain full color emission spectrum potentially.
Therefore, the application provides a kind of formula (I) compound
Or the definite compound containing two or three formula (I) unit be connected to each other via singly-bound or L group,
Wherein:
L is any divalence or trivalent organic group;
A is the group of the formula (A) via dotted line key bonding
Ar 1be identical or different in each case and be there are 5 to 30 aromatic ring atom and can by one or more R 1the aromatics that group replaces or heteroaromatic ring system;
Y is identical or different in each case and is singly-bound, BR 1, C (R 1) 2, Si (R 1) 2, NR 1, PR 1, P (=O) R 1, O, S, S=O or S (=O) 2;
B is identical or different in each case and is selected from the group of described formula (A), H, D, the alkyl group of the linear alkyl groups with 1 to 20 carbon atom or the side chain with 3 to 20 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, the one or more CH wherein in above-mentioned group 2group can by-R 1c=CR 1-,-C ≡ C-, Si (R 1) 2, C=O, C=NR 1,-C (=O) O-,-C (=O) NR 1-, NR 1, P (=O) (R 1) ,-O-,-S-, SO or SO 2replace, and have aromatics or the heteroaromatic ring system of 5 to 30 aromatic ring atom, each in described ring system can by one or more R 1group replaces;
R abe identical or different in each case and be F, CF 3, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1, the alkyl group of the linear alkyl groups with 1 to 20 carbon atom or the side chain with 3 to 20 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, and the one or more CH wherein in above-mentioned group 2group can by-R 1c=CR 1-,-C ≡ C-, Si (R 1) 2, C=O, C=NR 1,-C (=O) O-,-C (=O) NR 1-, NR 1, P (=O) (R 1) ,-O-,-S-, SO or SO 2replace, or there are 6 to 30 aromatic ring atom and can by one or more R 1the aromatics ring system that group replaces, or not via theheterocyclic nitrogen atom bonding and can by one or more R 1the heteroaromatic ring system with 5 to 30 aromatic ring atom that group replaces, wherein R agroup can with R 1group connects and can form ring;
R bbe selected from H, D and above about R athe group listed, wherein R bgroup can with R 1group connects and can form ring;
R 1be identical or different in each case and be H, D, F, C (=O) R 2, CN, Si (R 2) 3, N (R 2) 2, P (=O) (R 2) 2, OR 2, S (=O) R 2, S (=O) 2r 2, have straight chained alkyl or the alkoxy base of 1 to 20 carbon atom, or have the side chain of 3 to 20 carbon atoms or the alkyl of ring-type or alkoxy base, wherein above-mentioned group can separately by one or more R 2group replaces and one or more CH wherein in above-mentioned group 2group can by-R 2c=CR 2-,-C ≡ C-, Si (R 2) 2, C=O, C=NR 2,-C (=O) O-,-C (=O) NR 2-, NR 2, P (=O) (R 2) ,-O-,-S-, SO or SO 2replace, or have aromatics or the heteroaromatic ring system of 5 to 30 aromatic ring atom, each in described ring system can by one or more R 2group replaces, wherein two or more R 1group can be connected to each other and can form ring;
R 2be identical or different in each case and be H, D, F, or have the aliphatic series of 1 to 20 carbon atom, aromatics or heteroaromatic organic radical, wherein one or more hydrogen atoms also can be replaced by D or F; Meanwhile, two or more R 2substituting group can be connected to each other and can form ring;
Its condition is at least one R agroup is selected from F, CF 3, CF 2h, CFH 2, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1with E group, described E group has 6 to 18 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-.
Heteroaromatic ring system via theheterocyclic nitrogen atom bonding is especially interpreted as referring to the derivative of carbazole, indeno carbazole, indolocarbazole, pyrroles and imidazoles, and they have the corresponding nitrogen atom bonding of free valency via it.
Aromatic yl group in the context of the present invention contains 6 to 60 aromatic ring atom; Heteroaryl groups in the context of the present invention contains 5 to 60 aromatic ring atom, and wherein at least one is heteroatoms.Described heteroatoms is preferably selected from N, O and S.This is basic definition.If such as indicate other preferred feature at aromatic ring atom or existing heteroatoms quantitative aspects in the description of the present invention, be then suitable for these preferred features.
Aromatic yl group or heteroaryl groups are interpreted as referring to simple aromatic ring herein, i.e. benzene, or simple heteroaromatic rings, such as pyridine, pyrimidine or thiophene, or condense the aromatics of (condensation) or many rings of heteroaromatic, such as naphthalene, phenanthrene, quinoline or carbazole.The simple aromatics that the aromatics condensing (condensation) in the present context or the many rings of heteroaromatic are condensed each other by two or more or heteroaromatic rings form.
Can be replaced by above-mentioned group separately and the aryl that can be connected with described aromatics or heteroaromatic system via any desired position or heteroaryl groups, be interpreted as especially referring to the group being derived from following material: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, perylene, fluoranthene, benzanthrene, benzophenanthrene, tetracene, pentacene, benzopyrene, furans, cumarone, isobenzofuran, diphenylene-oxide, thiophene, thionaphthene, different thionaphthene, dibenzothiophene, pyrroles, indoles, isoindole, carbazole, pyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, thiodiphenylamine, fen piperazine, pyrazoles, indazole, imidazoles, benzoglyoxaline, naphtho-imidazoles, phenanthro-imidazoles, pyridine-imidazole, pyrazine imidazoles, quinoxaline imidazoles, azoles, benzo azoles, naphtho- azoles, anthra azoles, phenanthro- azoles, different azoles, 1,2-thiazole, 1,3-thiazoles, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo pyrimidine, quinoxaline, pyrazine, azophenlyene, naphthyridines, azepine carbazole, benzo carboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- diazole, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1,3,5-triazines, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and diazosulfide.
Aromatic ring in the context of the present invention ties up in ring system containing 6 to 60 carbon atoms.Heteroaromatic ring system in the context of the present invention contains 5 to 60 aromatic ring atom, and wherein at least one is heteroatoms.Described heteroatoms is preferably selected from N, O and/or S.Aromatics in the context of the present invention or heteroaromatic ring system are interpreted as referring to the system that only need not contain aryl or heteroaryl groups, but wherein two or more aryl or heteroaryl groups can also pass through non-aromatic unit (being preferably less than 10% of non-H atom) bonding, this non-aromatic unit is such as sp 3the carbon of hydridization, silicon, nitrogen or Sauerstoffatom, sp 2the carbon atom of the carbon of hydridization or nitrogen-atoms or sp hydridization.Such as, wherein two or more aromatic yl groups by the alkyl of such as straight chain or ring-type, alkenyl or alkynyl group or the system that connected by silyl-group the same, such as 9, the system of 9'-spiral shell two fluorenes, 9,9'-diaryl fluorenes, triarylamine, diaryl ether, Stilbene etc. is also regarded as aromatics ring system in the context of the present invention.In addition, the wherein system that is connected to each other via singly-bound of two or more aryl or heteroaryl groups, such as, the such as system of xenyl, terphenyl or phenylbenzene triazine, is also regarded as aromatics in the context of the present invention or heteroaromatic ring system.
There is 5-60 aromatic ring atom and also can be replaced by group as hereinbefore defined in each case and aromatics or the heteroaromatic ring system of aromatics or heteroaromatic system can be connected to via any desired position, being especially interpreted as referring to the group derived from following material: benzene, naphthalene, anthracene, benzanthrene, phenanthrene, benzophenanthrene, pyrene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, even benzene, terphenyl, trimeric benzene, quaterphenyl, fluorenes, spiral shell two fluorenes, dihydro is luxuriant and rich with fragrance, dihydropyrene, tetrahydrochysene pyrene, cis or trans-indenofluorene, three polyindenes, different three polyindenes, spiral shell three polyindene, different three polyindenes of spiral shell, furans, cumarone, isobenzofuran, diphenylene-oxide, thiophene, thionaphthene, different thionaphthene, dibenzothiophene, pyrroles, indoles, isoindole, carbazole, indolocarbazole, indeno carbazole, pyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, thiodiphenylamine, fen piperazine, pyrazoles, indazole, imidazoles, benzoglyoxaline, naphtho-imidazoles, phenanthro-imidazoles, pyridine-imidazole, pyrazine imidazoles, quinoxaline imidazoles, azoles, benzo azoles, naphtho- azoles, anthra azoles, phenanthro- azoles, different azoles, 1,2-thiazole, 1,3-thiazoles, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo pyrimidine, quinoxaline, 1,5-naphthodiazine, 2,7-diaza pyrene, 2,3-diaza pyrene, 1,6-diaza pyrene, 1,8-diaza pyrene, 4,5-diaza pyrene, 4,5,9,10-tetra-Dan Za perylene, pyrazine, azophenlyene, fen piperazine, thiodiphenylamine, fluorubin, naphthyridines, azepine carbazole, benzo carboline, phenanthroline, 1,2,3-triazoles, 1,2,4-triazole, benzotriazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- diazole, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1,3,5-triazines, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetrazine, 1,2,3, the combination of 4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and diazosulfide or these groups.
In the context of the present invention, wherein independent hydrogen atom or CH 2the linear alkyl groups with 1 to 40 carbon atom that group also can be replaced by the group mentioned in described group definition above and there is the side chain of 3 to 40 carbon atoms or the alkyl group of ring-type and there is the alkenyl or alkynyl group of 2 to 40 carbon atoms, preferably be interpreted as referring to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, 2-methyl butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, neo-pentyl, n-hexyl, cyclohexyl, new hexyl, n-heptyl, suberyl, n-octyl, ring octyl group, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl group, 2, 2, 2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctene base, ethynyl, proyl, butynyl, pentynyl, hexin base or pungent alkynyl group.Alkoxyl group or the thioalkyl groups with 1 to 40 carbon atom are preferably interpreted as referring to methoxyl group, trifluoromethoxy, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, secondary pentyloxy, 2-methylbutoxy group, positive hexyloxy, cyclohexyloxy, positive heptan oxygen base, ring oxygen in heptan base, n-octyloxy, ring octyloxy, 2-ethyl hexyl oxy, five fluorine oxyethyl groups, 2,2,2-trifluoro ethoxy, methylthio group, ethylmercapto group, positive rosickyite base, isopropyisulfanyl, positive butylthio, isobutylthio, secondary butylthio, tertiary butylthio, positive penta sulfenyl, secondary penta sulfenyl, just own sulfenyl, cyclohexylthio, positive heptan sulfenyl, ring sulfenyl in heptan, just pungent sulfenyl, cyclooctasulfur base, 2-ethyl hexyl sulfenyl, trifluoromethylthio, five fluorine ethylmercapto groups, 2,2,2-trifluoro ethylmercapto group, ethene sulfenyl, propylene sulfenyl, butylene sulfenyl, amylene sulfenyl, cyclopentenes sulfenyl, hexene sulfenyl, tetrahydrobenzene sulfenyl, heptene sulfenyl, suberene sulfenyl, octene sulfenyl, cyclooctene sulfenyl, acetylene sulfenyl, propine sulfenyl, butine sulfenyl, pentyne sulfenyl, hexin sulfenyl, heptyne sulfenyl or octyne sulfenyl.
In the context of this application, the word that two or more groups can form ring is together interpreted as referring in particular to two groups and is connected to each other by chemical bond.This is by lower illustrated example:
But in addition, above-mentioned word is also interpreted as referring to, if one of two groups are hydrogen, then the second group bonding is to the position of hydrogen atom institute bonding, from forming ring.This will by lower illustrated example:
L group is preferably selected from the divalent group of following group: the alkylidene group with 1 to 20 carbon atom, wherein one or more CH 2group can by Si (R 1) 2, O, S, C=O, C=NR 1, C=O-O, C=O-NR 1, NR 1, P (=O) (R 1), SO or SO 2replace and described alkylidene group can by one or more R 1group replaces, or has aromatics or the heteroaromatic ring system of 5 to 30 aromatic ring atom, and each in described ring system can by one or more R 1group replaces; Or for being selected from the trivalent radical of aromatics or the heteroaromatic ring system with 5 to 30 aromatic ring atom, each in described group can by one or more R 1group replaces.
Formula (A) preferably meets following formula (A-1) to one of (A-22), and it is via dotted line key bonding:
Wherein:
X is identical or different in each case and is CR 1or N;
U is BR 1, C (R 1) 2, Si (R 1) 2, NR 1, O or S; With
R 1as hereinbefore defined.
In formula (A-1) in (A-22), preferred formula (A-1), (A-4), (A-14) and (A-17).
When U is C (R 1) 2or Si (R 1) 2during group, preferably, two R in described group 1group is connected to each other and forms ring.This is preferably formed five yuan or six-ring.This more preferably forms spiral shell two fluorene group.
For above formula preferably X be CR 1.
Be N for being no more than three X group in above formula preferably each ring in addition.Preferably being no more than two adjacent X group in addition in a ring is N.More preferably, the definite X group of each ring is N, or is N without X group in ring.
Preferably, the U group in above formula is C (R 1) 2or NR 1, be more preferably C (R 1) 2.
Particularly preferably above-mentioned preferred implementation combination each other.
Preferably, Ar 1be identical or different in each case and be there are 6 to 20 aromatic ring atom and can by one or more R 1the aromatics ring system that group replaces, and is more preferably phenyl, pyridyl, naphthyl, fluorenyl or carbazyl, and each in described group can by one or more R 1group replaces.
Preferably, Y group is identical or different in each case and is singly-bound, C (R 1) 2, NR 1, O or S, be more preferably singly-bound.
For B group, according to the present invention preferably, it is identical or different in each case and is selected from formula (A) group, H, the alkyl group of the linear alkyl groups with 1 to 10 carbon atom or the side chain with 3 to 10 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, or has the aromatic yl group of 6 to 14 aromatic ring atom, and each in described group can by one or more R 1group replaces.When described B group is selected from formula (A) group, preferably it is selected from the group of formula (A-1) to (A-22).
More preferably, described B group is identical or different in each case and is formula (A) group or H.Most preferably, described B group is formula (A) group.When described B group is formula (A) group, preferably it is selected from the group of formula (A-1) to (A-22).
According to R aand R bdefinition, it is evident that these can not be carbazole via nitrogen atom bonding or carbazole derivative.
For R agroup, according to the present invention, preferably, it is identical or different in each case and is selected from F, CF 3, CN, the alkyl group of the linear alkyl groups with 1 to 10 carbon atom or the side chain with 3 to 10 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, or has 6 to 14 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, wherein said heteroaryl groups is not via nitrogen atom bonding, and its condition is at least one R agroup is selected from F, CF 3, CN and E group, described E group has 6 to 14 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-.
More preferably, two R agroup is identical or different and is selected from F, CF 3, CN and E group, described E group has 6 to 14 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-.Described heteroaryl groups is not via nitrogen atom bonding.
Preferably, in E group, there are at least two V groups, more preferably two, three, four or five V groups.
Described E group is preferably via the group of the formula (E-1) to (E-9) of dotted line key bonding.
Wherein:
W is identical or different in each case and is CR 1or V, wherein at least one W group is V; With
Wherein V and R 1separately as hereinbefore defined.
In the group of formula (E-1) to (E-9), the group of preferred formula (E-1).
Preferably, in the group of formula (E-1) to (E-9), at least two W groups are V, are more preferably definite two, three, four or five W groups are V.
In addition preferably, in ring, have that to be no more than two adjacent one another are be the=V group of N-.In addition preferably, in ring, have that to be no more than three be=V the group of N-.
The particularly preferably embodiment of described E group meets following formula (E-1-1) to (E-1-89)
Preferably, R bbe identical or different in each case and be selected from H, F, CF 3, CN, the alkyl group of the linear alkyl groups with 1 to 10 carbon atom or the side chain with 3 to 10 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, and has aryl or the heteroaryl groups of 6 to 14 aromatic ring atom, and each in described group can by one or more R 1group replaces, and wherein said heteroaryl groups is not via nitrogen atom bonding.More preferably, R bbe identical or different in each case and be selected from H, F, CF 3, CN and E group as hereinbefore defined.
Preferably, R 1group is identical or different in each case and is H, D, F, CN, Si (R 2) 3, N (R 2) 2, have straight chained alkyl or the alkoxy base of 1 to 10 carbon atom, or have the side chain of 3 to 10 carbon atoms or the alkyl of ring-type or alkoxy base, wherein above-mentioned group can separately by one or more R 2group replaces and one or more CH wherein in above-mentioned group 2group can by-R 2c=CR 2-,-C ≡ C-, Si (R 2) 2, C=O, C=NR 2,-C (=O) O-,-C (=O) NR 2-, NR 2, P (=O) (R 2) ,-O-,-S-, SO or SO 2replace, or have aromatics or the heteroaromatic ring system of 5 to 20 aromatic ring atom, each in described ring system can by one or more R 2group replaces, wherein two or more R 1group can be connected to each other and can form ring.
The preferred implementation of described formula (I) compound meets formula (I-1) to (I-3)
Wherein H, D, there is the alkyl group of 1 to 10 carbon atom or there is aromatics or the heteroaromatic ring system of 6 to 30 aromatic ring atom, wherein each can by one or more R 1group replaces, and is optionally bonded to not planting oneself on the phenyl ring in formula (I-2), and
Wherein A, R aand R bseparately as hereinbefore defined, and condition is at least one R to group agroup is selected from F, CF 3, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1with E group, described E group has 6 to 18 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-.Preferably, described condition is applicable to two R agroup.
Preferably A, B and R in addition aand R bpreferred implementation particularly with the combination of formula (I-1) to (I-3).
Particularly preferably, in formula (I-1) in (I-3), described A group meets formula (A-1) as hereinbefore defined to one of (A-22).
The particularly preferably embodiment of described formula (I) compound is the compound of formula (I-1-a) to (I-1-f)
Wherein:
X be as hereinbefore defined and preferably CR 1;
R aand R bseparately as hereinbefore defined; With
Its conditional is at least one R agroup is selected from F, CF 3, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1with E group, described E group has 6 to 18 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-, and wherein said condition optimization is applicable to two R agroup.
Preferably, R aand R bbe identical or different in each case and be F, CF 3, CN or E group as hereinbefore defined.
The particularly preferably embodiment of described formula (I) compound is the compound of formula (I-2-a) to (I-2-f)
Wherein H, D, there is the alkyl group of 1 to 10 carbon atom or there is aromatics or the heteroaromatic ring system of 6 to 30 aromatic ring atom, wherein each can by one or more R 1group replaces, and is optionally bonded to formula (I-2-1) to not planting oneself on the phenyl ring in (I-2-f), and
Wherein:
X be as hereinbefore defined and preferably CR 1;
R aand R bseparately as hereinbefore defined to; With
Its conditional is at least one R agroup is selected from F, CF 3, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1with E group, described E group has 6 to 18 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-, and wherein said condition optimization is applicable to two R agroup.
Preferably, R aand R bbe identical or different in each case and be F, CF 3, CN or E group as hereinbefore defined.
The particularly preferably embodiment of described formula (I) compound is the compound of formula (I-3-a) to (I-3-f)
Wherein:
X be as hereinbefore defined and preferably CR 1;
R aas hereinbefore defined; With
Its conditional is at least one R agroup is selected from F, CF 3, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1with E group, described E group has 6 to 18 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-, and wherein said condition optimization is applicable to two R agroup.
Preferably, R abe identical or different in each case and be F, CF 3, CN or E group as hereinbefore defined.
Hereafter describe the example according to compound of the present invention:
Known organic chemical synthesis step such as bromination, boronation, nucleophilic aromatic replacement and transition metal-catalyzed linked reaction such as Buchwald coupling can be used to prepare described formula (I) compound.
Scheme 1 illustrates the illustrative methods for the preparation of formula (I) compound, and it carries out from the cyano group substitution compound (can buy in many cases) with one or more fluoro substituents.In this approach, one or more carbazole derivative of introducing are replaced by nucleophilic aromatic.Described method can progressively realize, and therefore first can introduce a kind of carbazole derivative, then then introduces another kind of different carbazole derivative (see bottom line (s.untereZeile)).Other electron-withdrawing group can be used to replace CN.According to the substituting group defined in claim 1, shown compound can have any desired further replacement.This sets forth all schemes of synthetic method below being applicable to.
Scheme 1
In addition, also by Buchwald coupling, carbazole derivative is introduced in compound of the present invention.This in scheme 2 about with CF 3the compound citing display of group.But, other group can be there is in addition as CN or F or electron deficiency heteroaromatics but not CF 3.
Scheme 2
Alternative method for the scheme 2 introducing carbazole derivative is shown in scheme 3.This carries out from nitrobenzene derivative, and it is converted into aminophenyl derivative, then enters the dual Buchwald coupling with suitable halogen substiuted dibenzyl.Also can there is other group, such as F, CF 3or CN, instead of shown C 6f 5group.
Scheme 3
Can to be prepared in the compound that there is carbazole derivative with electrophilic heteroaromatic system adjacent position as shown in hereafter scheme 4.For this purpose, raw material is the carbazole phenyl derivative with halogenic substituent or another kind of suitable leavings group.This converting compounds is boric acid, and in the second step, then it carry out Suzuki coupling with electron deficiency aromatic systems.By dual Suzuki coupling, the compound with two different heteroaryl substituent can be prepared.
Scheme 4
Synthetic method is above that those of ordinary skill in the art are about the thinking how can preparing the compounds of this invention in the gamut of the application's claim.Those of ordinary skill in the art with reference to the specific embodiment existed in the application for illustrating further.It is using the general technology knowledge utilized in addition about organic chemical synthesis method and utilize commercial compound as raw material, to prepare the compounds of this invention clearly not describing synthesis in this document.In addition, in the scope of its general technical knowledge, method described herein (if this brings real advantage) can be revised.
Generally speaking, the invention provides the method for a kind of preparation formula (I) compound, it is characterized in that being replaced by nucleophilic aromatic or at least one carbazole derivative is introduced in Buchwald coupling, or be characterised in that and introduce at least one electron deficiency heteroaryl groups by Suzuki coupling.Preferred concrete synthetic method detailed above.
The compounds of this invention, especially by the compound that reactive leavings group replaces as bromine, iodine, chlorine, boric acid or boric acid ester, can be used as the monomer for the preparation of corresponding oligopolymer.Suitable reactive leavings group is such as bromine, iodine, chlorine, boric acid, boric acid ester, amine, there is the alkenyl or alkynyl group of end C-C double bond or C-C triple bond, oxyethane, trimethylene oxide, enters cycloaddition such as 1, the group of 3-dipole-diople interaction, such as diene or trinitride, carboxylic acid derivative, alcohol and silane.
Therefore, the present invention also provides the oligopolymer containing one or more formulas (I) compound, and wherein one or more keys forming described oligopolymer can be arranged in formula (I) by R 1or R 2any position replaced.According to the connection of formula (I) compound, described compound is the integral part of the side chain of oligopolymer or the integral part of main chain.Oligopolymer is in the context of the present invention interpreted as referring to by least four monomeric units and the compound that formed of nine monomeric units at the most.Oligopolymer of the present invention can be conjugation, partly conjugated or unconjugated.Oligopolymer of the present invention can be straight or branched.In the structure with straight chain connection, the unit of formula (I) can be connected to each other directly, or they via divalent group, such as, via substituted or unsubstituted alkylidene group, can be connected to each other via heteroatoms or via divalent aromatic or heteroaromatic group.In branched structure, such as, three or more formula (I) unit by trivalent or more high price group, such as via trivalent or more high price aromatics or heteroaromatic group connect, obtain branched oligomer.
For the repeating unit of the formula (I) in oligopolymer, be suitable for above about preferred feature identical described in formula (I) compound.
Oligopolymer of the present invention is prepared, wherein the repeating unit of at least one monomer production (I) in oligopolymer by the oligomeric of one or more monomer types.For the preparation of oligopolymer, make monomer of the present invention such as homopolymerization or with other monomer copolymerization.Suitable oligomerization is known to persons of ordinary skill in the art and is described in document.
But, described oligopolymer can also be prepared by progressively organic synthesis.
Oligopolymer of the present invention has favourable characteristic, especially high life, high-level efficiency and good color coordinates.
Described formula (I) compound is suitable for electron device, particularly in organic electroluminescence device (OLED).Depend on replacement, described formula (I) compound may be used in difference in functionality and layer.Be preferred in luminescent layer, be more preferably used as the luminophor in luminescent layer.
Therefore, the present invention also provides the purposes of formula (I) compound in electron device.This electron device is preferably selected from organic integrated circuits (OIC), organic field effect tube (OFET), OTFT (OTFT), organic light-emitting transistor (OLET), organic solar batteries (OSC), organic optical detector, organophotoreceptorswith, organic field quenching device (OFQD), organic light emission electrochemical cell (OLEC), organic laser diode (O-laser), and is more preferably organic electroluminescence device (OLED).
The present invention goes back the electron device of providing package containing at least one formula (I) compound.This electron device is preferably selected from above-mentioned device.
Particularly preferably comprise the organic electroluminescence device of anode, negative electrode and at least one luminescent layer, it is characterized in that in described device, there is at least one organic layer comprising at least one formula (I) compound.Preferably comprise the organic electroluminescence device of anode, negative electrode and at least one luminescent layer, to it is characterized in that in described device that the organic layer that at least one is selected from luminescent layer comprises at least one formula (I) compound.
Except negative electrode, anode and luminescent layer, described electron device also can comprise other layer.These layers are such as selected from one or more hole injection layer, hole transmission layer, hole blocking layer, electron transfer layer, electron injecting layer, electronic barrier layer, exciton barrier-layer, middle layer, charge generation layer (IDMC2003, Taiwan in each case; Session21OLED (5), T.Matsumoto, T.Nakada, J.Endo, K.Mori, N.Kawamura, A.Yokoi, J.Kido, MultiphotonOrganicELDeviceHavingChargeGenerationLayer (there is the multi-photon OLED device of charge generation layer)) and/or organic or inorganic p/n tie.But to it should be pointed out that in these layers each not must exist, and the compound of use is depended in the selection of layer usually, and particularly also depends on that described device is fluorescigenic or phosphorescent electroluminescent device.
The order of the layer in described electron device is preferably as follows:
-anode-
-hole injection layer-
-hole transmission layer-
-optionally other hole transmission layer-
-luminescent layer-
-electron transfer layer-
-electron injecting layer-
-negative electrode-.
And the described layer of not all must exist, and other layer can be there is in addition.
Those of ordinary skill in the art know the suitable combination thing that can be used in equivalent layer according to technical literature.
The preferred negative electrode of described electron device has the metal of low work function, metal alloy or multilayered structure, and it is made up of different metal such as alkaline-earth metal, basic metal, main group metal or lanthanon (such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm etc.).The alloy be it is suitable that made up of with silver basic metal or alkaline-earth metal in addition, the alloy be such as made up of magnesium and silver.In multilayered structure situation, except described metal, also can use other metal such as Ag or Al with relatively high work function, in this case, usually use the combination of metal, such as Ca/Ag, Mg/Ag or Ba/Ag.Also the thin middle layer with the material of high-k can preferably be introduced between metallic cathode and organic semiconductor.The example being applicable to the material of this object is alkaline metal fluoride cpd or alkaline-earth metal fluoride, but also can be corresponding oxide compound or carbonate (such as LiF, Li 2o, BaF 2, MgO, NaF, CsF, Cs 2cO 3deng).In addition, for this purpose, hydroxyquinoline lithium (LiQ) can be used.
Preferred anode is the material with high work function.Preferably, described anode has the work function being greater than 4.5eV relative to vacuum.First, the metal with high redox potential is suitable for this object, such as Ag, Pt or Au.On the other hand, also can preferable alloy/metal oxide electrode (such as Al/Ni/NiO x, Al/PtO x).For some application, at least one electrode must be transparent or partially transparent, to realize organic materials radiation (organic solar batteries) or luminous (OLED, O-laser).Preferred anode material is electroconductibility mixed metal oxide herein.Particularly preferably tin indium oxide (ITO) or indium zinc oxide (IZO).In addition preferred electroconductibility doping organic materials, particularly electroconductibility doped polymer.In addition, described anode also can be made up of two or more layers, such as, be made up of the skin of ITO internal layer and metal oxide (preferential oxidation tungsten, molybdenum oxide or vanadium oxide).
If described formula (I) compound is used as the luminophor in luminescent layer, then preferred matrix compounds is as hereinbefore defined present in described layer as another kind of component.In this case; matrix compounds used can be the compound that those of ordinary skill in the art become known for this object; such as 4; 4'-(two carbazole-9-base) biphenyl (CBP) or 2; two (diphenylphosphoryl) dibenzo [b, the d] thiophene (PPT) of 8-.
In addition, when being used as luminophor, described compound is preferably present in luminescent layer with the ratio of 0.1 volume % to 50.0 volume %, more preferably 0.5 volume % to 20.0 volume % and most preferably 0.5 volume % to 8.0 volume %.
Those of ordinary skill in the art know the method being suitable for manufacturing electron device.More specifically, after using described layer, described device is by suitably (according to application) structurizing, and contact connects and finally sealed, to get rid of the destruction of water and air.
The electron device comprising one or more formulas (I) compound can be particularly useful in indicating meter, the light source being used as the light source in illumination application and being used as in medical treatment or cosmetic application (such as actinotherapy).
Embodiment
A) synthetic example:
Unless otherwise indicated, otherwise following synthesis carry out in anhydrous solvent under protective gas atmosphere.Lucifuge or process metal complex under gold-tinted in addition.Solvent and reagent can purchased from such as Sigma-ALDRICH or ABCR.
I) synthesis of the compounds of this invention:
Embodiment S1:1,3,5-tricyano-2,4,6-tri-(N-carbazyl) benzene
Modification A:
At about+10 DEG C, the carbazole [51555-21-6] adding 66.9g (400mmol) by part in well-beaten suspension in 500mLTHF of the sodium hydride (60 % by weight dispersions in mineral oil) of 16.0g (400mmol) (is noted with while ice-cooled! Hydrogen is overflowed! Bubble! ).After interpolation terminates, mixture is stirred 30 minutes again, then in the mode making temperature be no more than+20 DEG C with 1,3,5-tricyano-2,4, the 6-trifluoro-benzene [363897-9] adding 20.7g (100mmol) while ice-cooled by part.After interpolation terminates, mixture is stirred 2 hours again at+10 DEG C, then removes cooling bath, and make mixture be warming up to 20-25 DEG C, then stir 2 hours, be then heated to 40 DEG C and continue 12 hours again.After cooling to room temperature, carry out termination reaction by dropwise adding 30mLMeOH, and under reduced pressure reaction mixture is almost concentrated into dry.Utilize the 600mL mixture of each 400mL methyl alcohol and 200mL water to carry out extraction heat to resistates and stir twice, then carry out extraction heat with 500mL methyl alcohol and stir once.By from two recrystallization three times in alkane (about 5mL/g), then from DMF (about 2.5mL/g) recrystallization five times and fractional sublimation twice (p is about 1 × 10 -5millibar, T is about 310-320 DEG C) realize purifying.Productive rate: 23.6g (36.3mmol) 36%.Purity: 99.9%, according to HPLC.
Variant B:
The step similar with modification A, difference is first in THF, to load carbazole, then dropwise adds the n-BuLi (2.5M is in normal hexane) of 160mL (400mmol).
Productive rate: 19.0g (29.3mmol) 29%.Purity: 99.9%, according to HPLC.
Variant C:
By the carbazole [51555-21-6] of 66.9g (400mmol), 1 of 20.7g (100mmol), 3,5-tricyano-2, the Tripotassium phosphate (anhydrous) of 4,6-trifluoro-benzene, 106.1g (500mmol) and the well-beaten suspension of 200g glass beads stir 16 hours in 500mL N,N-DIMETHYLACETAMIDE at 160 DEG C.After the cooling period, add 1000mL water, filter out the solid of precipitation, and by these with each 300mL water washing twice and by each 200mL methanol wash twice, then drying under reduced pressure.Be further purified similarly with modification A.Productive rate: 20.5g (31.6mmol) 31%.Purity: 99.9%, according to HPLC.
In a similar fashion, following compound can be prepared:
Embodiment S64:1,3,5-tricyano-2-(N-carbazyl)-4,6-pairs-(N-3,6-phenylbenzene carbazyl) benzene, S64
At about+10 DEG C, the carbazole [51555-21-6] adding 16.7g (100mmol) by part in well-beaten suspension in 500mLTHF of the sodium hydride (60 % by weight dispersions in mineral oil) of 4.0g (100mmol) (is noted with while ice-cooled! Hydrogen is overflowed! Bubble! ).After interpolation terminates, mixture is stirred 30 minutes again, then while ice-cooled, adds 20.7g (100mmol) 1,3 by part in the mode making temperature be no more than+20 DEG C, fluoro-4, the 6-dichlorobenzene [25751-93-7] of 5-tricyano-2-.After interpolation terminates, mixture is stirred 2 hours again at+10 DEG C, then removes cooling bath, and make mixture be warming up to 20-25 DEG C, then stir 2 hours, be then heated to 40 DEG C and continue 6 hours again.After cooling to room temperature, add the sodium hydride (60 % by weight dispersions in mineral oil) of 12.0g (300mmol), reaction mixture is cooled to+10 DEG C, then 3,6-phenylbenzene carbazoles [the 56525-79-2] (attention of 95.8g (300mmol) is added by part! Hydrogen is overflowed! Bubble! ).After interpolation terminates, mixture is stirred 2 hours again at+10 DEG C, then removes cooling bath, and make mixture be warming up to 20-25 DEG C, then stir 2 hours, be then heated to 60 DEG C and continue 16 hours again.After cooling to room temperature, carry out termination reaction by dropwise adding 30mLMeOH, and then under reduced pressure reaction mixture is almost concentrated into dry.Utilize the 600mL mixture of each 400mL methyl alcohol and 200mL water to carry out extraction heat to resistates and stir twice, then carry out extraction heat with 500mL methyl alcohol and stir once.By from two recrystallization three times in alkane (about 3.5mL/g), then from DMF (about 2mL/g) recrystallization five times and fractional sublimation twice (p is about 1 × 10 -5millibar, T is about 330-340 DEG C) realize purifying.Productive rate: 22.9g (24.0mmol) 24%.Purity: 99.9%, according to HPLC.
In a similar manner, following compound is prepared:
II) synthesis of precursor
Embodiment S72-V:9-(2,6-dibromo phenyl)-9H-carbazole
The well-beaten suspension of 1, the 3-bis-bromo-2-fluorobenzene [363897-9] of the carbazole [51555-21-6] of 66.9g (400mmol), 25.4g (100mmol), the Tripotassium phosphate (anhydrous) of 106.1g (500mmol) and 200g glass beads is stirred 16 hours in 500mL N,N-DIMETHYLACETAMIDE at 160 DEG C.After the cooling period, add 1000mL water, filter out the solid of precipitation, and by these with each 300mL water washing twice and by each 200mL methanol wash twice, then drying under reduced pressure.After single recrystallization from toluene/heptane, obtain 18.9g (47.2mmol, 47%) and then transform further.
Transform similarly following:
Embodiment S74-V:9-[the bromo-6-of 2-(4,4,5,5-tetramethyl--[1,3,2] dioxy boron penta cyclic group) phenyl]-9H-carbazole
First by 18.5 (46.1mmol, 1 equivalent) S72-V and 14.1g (55.3mmol, 1.2 equivalents) two (tetramethyl ethylene ketone foundation) diboron hexahydride (CAS73183-34-3) and 15.8g (161mmol, 3.5 equivalents) potassium acetate (CAS127-08-2) load together in 100mLTHF, and after degassing, add 1,1-two (diphenylphosphino) ferrocene dichloro palladium (II) of 2.26g (0.06 equivalent) and the complex compound (CAS95464-05-4) of DCM.Mixture is heated 14 hours under reflux, and after the completion of reaction, adds water.Removing organic phase and by methylene dichloride aqueous phase extracted repeatedly.The organic phase of merging is under reduced pressure removed solvent through dried over sodium sulfate.Obtain the product S 74-V of 15.3g (34.1mmol, 74%).
Transform similarly following:
Embodiment S76-V:9-[the bromo-6-of 2-(4,6-phenylbenzene-[1,3,5] triazine-2-base) phenyl]-9H-carbazole, S76-V
Modification A
2-chloro-4, the 6-phenylbenzene-1,3,5-triazines (CAS3842-55-5) of S74-V, 11.6g (43.5mmol, 1.3 equivalents) of 15.0g (33.5mmol) and the sodium carbonate of 5.3g are suspended in 200mL bis- in alkane, 200mL toluene and 100mL water.Pd (the PPh of 1.94g (1.68mmol, 0.05 equivalent) is added in this suspension 3) 4.By reaction mixture heated overnight under reflux.After the cooling period, suction filtration goes out the solid of precipitation, by water and washing with alcohol, and dry.Toluene extraction heat is carried out to resistates and from toluene/heptane recrystallization.Obtain the product S 76-V of 7.23g (13.1mmol, 39%).
Transform similarly following:
III) synthesis of the compounds of this invention and precursor:
Embodiment S78:9-[3-(4,6-phenylbenzene-[1,3,5] triazine-2-base)-biphenyl-2-base]-9H-carbazole
The phenyl-boron dihydroxide (CAS98-80-6) of S76-V, 1.72g (14.1mmol, 1.1 equivalents) of 7.1g (12.8mmol) and the Tripotassium phosphate of 5.45g (25.7mmol, 2 equivalents) are dissolved in 100mL bis- in alkane, 100mL toluene and 50mL water, and degassed 30 minutes.Subsequently, add 86mg (0.38mmol, 0.03 equivalent) acid chloride (II) and 230mg (0.77mmol, 0.06 equivalent) tri-o-tolyl phosphine and mixture is heated to reflux.After the completion of reaction, mixture is cooled, and removes aqueous phase and extract repeatedly with toluene.By the organic phase washed with water of merging and through dried over sodium sulfate, and under reduced pressure remove solvent.Toluene extraction heat is carried out to resistates and from toluene/heptane recrystallization.After distillation, obtain the required product S 78 of 4.1g (7.4mmol, 58%), its HPLC purity >99.9%.
IV) synthesis of precursor:
Two (trifluoromethyl) biphenyl of bromo-2,3,4,5,6-five fluoro-3', the 5'-of embodiment S81-V:4'-
To 2 of 11.4g (30mmol), 3,4,5, under lucifuge, the bromine of 1.7mL (32mmol) and the mixture of 20mL chloroform is dropwise added in the solution of two (trifluoromethyl) biphenyl [1363958-46-6] of 6-five fluoro-3', 5'-in 300mL methylene dichloride.Stir at 40 DEG C after 16 hours, add 200mL ethanol and 50mL saturated sodium bisulfite solution successively.Suction filtration goes out colorless solid, and with 200mL water washing three times and by 100mL washing with alcohol three times, drying under reduced pressure, then by recrystallization in DMF and toluene and isomer separation.Productive rate: 4.1g (9mmol), 30% of theoretical value.
In a similar manner, following compound can be obtained:
V) synthesis of the compounds of this invention:
Embodiment S91:9-(2,6-3,5-dimethylphenyl)-9H-[3,9'] joins carbazole
The 9H-[3,9'] of 12.6g (38.32mmol) is joined carbazole [18628-07-4], bromo-1, the 3-di-trifluoromethyl benzene [118527-30-3] of 2-of 7g (38.32mmol) and the K of 16g 2cO 3be suspended in 300mL p-Xylol.The Pd (OAc) of 0.86g (3.84mmol) is added in described suspension 2with the 1M tri-butyl phosphine solution of 7.6mL.Reaction mixture is heated 16 hours under reflux.After the cooling period, organic phase is removed, with 200mL water washing three times, is then concentrated into dry.Toluene extraction heat is carried out to resistates, recrystallization from toluene and finally distilling under a high vacuum.Productive rate: 14.5g (35mmol), 87% of theoretical value; Purity 99.9%.
In a similar manner, following compound can be obtained:
VI) synthesis of precursor
The fluoro-3-trifluoromethyl-biphenyl of embodiment S106-V:2', 3', 4', 5', 6'-five-2-base amine
First 2 of 294mL concentrated hydrochloric acid, 700mL ethanol and 38g (126mmol) is loaded, 3,4,5, the fluoro-2'-nitro of 6-five-3'-trifluoromethyl-biphenyl [1261680-28-7], and the glass putty at room temperature adding 35g (294mmol) by part.After interpolation, mixture is at room temperature stirred 3 hours.Thereafter, by reaction mixture being adjusted to pH=12 with adding NaOH (solid) while ice-cooled.Filter out resistates, recrystallization by washed with dichloromethane and from heptane.This obtains the white solid of 22g (79mmol), corresponding to 63% of theoretical value.
In a similar manner, the glass putty of 2 equivalents is utilized can to obtain following compound:
VII) synthesis of the compounds of this invention:
Embodiment S109:9-(3,2', 3', 4', 5', 6'-hexafluoro biphenyl-2-base)-9H-carbazole
By three (dibenzalacetone) two palladium (0) of 2, the 2'-'-dibromobiphenyls of 15.6g (50mmol) and 500mL toluene, 2.3g (2.5mmol), the 1Mt-Bu of 10mL 3p is blended in the sodium tert-butoxide of toluene and 11.5g (120mmol).Subsequently, the 2' of 11.8g (40mmol) is added, the fluoro-3-trifluoromethyl-biphenyl of 3', 4', 5', 6'-five-2-base amine.Mixture is heated to 110 DEG C and continues 20 hours, be then cooled to room temperature, and add 400mL water.Be extracted with ethyl acetate mixture, then the organic phase of merging also under reduced pressure concentrated through dried over sodium sulfate.Make resistates from toluene neutralization recrystallization from methylene dichloride/Virahol, and finally distil under a high vacuum.Purity is 99.9%.Productive rate is 10g (23mmol), corresponding to 59% of theoretical value.
In a similar manner, following compound can be obtained:
B) device embodiments
In the examples below, the result using the compounds of this invention as the various OLED of luminophor is presented.
The sheet glass having used structurizing ITO (tin indium oxide) to be coated with is the substrate of OLED.Wet-cleaning (cleaner, washing composition: Merck Extran) is carried out to described substrate, then toasts 15 minutes at 250 DEG C, and subsequent coating, use oxygen plasma treatment.
All material is applied in a vacuum chamber by thermal vapor deposition.Luminescent layer is always made up of substrate material and luminescent material.By coevaporation, the latter is added into substrate material with designated volume ratio.
Characterize described OLED in the standard fashion.At 1000cd/m 2brightness under measure electroluminescent spectrum, and calculate CIE1931x and y color coordinates thus.In addition, 1000cd/m is measured 2the voltage needed for brightness.Table 1 reports in addition at 1000cd/m 2the external quantum efficiency that is issued to of operating brightness.This measures based on hypothesis youth uncle radiation characteristic.
1 type
Substrate:
ITO，50nm
Hole injection layer/hole transmission layer:
Two [N-(1-the naphthyl)-N-phenyl amino] biphenyl of 4,4-, α-NPD, [123847-85-8], 90nm
Luminescent layer:
Two (N-carbazole) the biphenyl CBP of 4,4'-, [58328-31-7], as substrate material, doped with the compounds of this invention (see table 1) of 5 volume % as doping agent, 15nm
Electron transfer layer:
1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene TPBi, [192198-85-9], 50nm
Electron injecting layer:
LiF，1nm
Negative electrode:
Al，100nm
1a type
The structure identical with 1 type, difference is to use thickness to be 120 but not α-NPD the layer of 90nm and thickness are 60 but not the TPBI layer of 50nm.
2 types
Substrate:
ITO，50nm
Hole injection layer/hole transmission layer:
Two [N-(1-the naphthyl)-N-phenyl amino] biphenyl of 4,4-, α-NPD, [123847-85-8], 80nm
Hole transmission layer:
Two (9-carbazyl) benzene of 1,3-, mCP, [550378-78-4], 10nm
Luminescent layer:
Two (diphenylphosphoryl) dibenzo [b, the d] thiophene of 2,8-, PPT, [1019842-99-9], and as substrate material, doped with the compounds of this invention (see table 1) of 5 volume % as doping agent, 20nm
Electron transfer layer:
Two (diphenylphosphoryl) dibenzo [b, the d] thiophene of 2,8-, PPT, [1019842-99-9], 50nm
Electron injecting layer:
LiF，1nm
Negative electrode:
Al，100nm
The compounds of this invention in OLED as the purposes of luminiferous material
The compounds of this invention especially can be used as luminiferous material in the luminescent layer of OLED.Be summarized in table 1 about the value measured by power efficiency, voltage and color coordinates.
Table 1:
Manufactured OLED shows excellent power efficiency values.By using different twinklers, the light with distinct colors coordinate can be obtained.
Show with the comparing of compound (contrast in P-V1 and P-V2 1 and contrast 2) according to prior art, by replacing these compounds with the compounds of this invention, under similar voltage, power efficiency obtains outstanding improvement.
The compound of comparative example P-1 and P-V2:

Claims (15)

1. the compound of formula (I)
Or the compound containing two or three formula (I) unit be connected to each other via singly-bound or L group definite,
Wherein:
L is any divalence or trivalent organic group;
A is the group of the formula (A) via dotted line key bonding
Ar 1be identical or different in each case and be there are 5 to 30 aromatic ring atom and can by one or more R 1the aromatics that group replaces or heteroaromatic ring system;
Y is identical or different in each case and is singly-bound, BR 1, C (R 1) 2, Si (R 1) 2, NR 1, PR 1, P (=O) R 1, O, S, S=O or S (=O) 2;
B is identical or different in each case and is selected from the group of described formula (A), H, D, the alkyl group of the linear alkyl groups with 1 to 20 carbon atom or the side chain with 3 to 20 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, the one or more CH wherein in above-mentioned group 2group can by-R 1c=CR 1-,-C ≡ C-, Si (R 1) 2, C=O, C=NR 1,-C (=O) O-,-C (=O) NR 1-, NR 1, P (=O) (R 1) ,-O-,-S-, SO or SO 2replace, and have aromatics or the heteroaromatic ring system of 5 to 30 aromatic ring atom, each in described ring system can by one or more R 1group replaces;
R abe identical or different in each case and be F, CF 3, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1, the alkyl group of the linear alkyl groups with 1 to 20 carbon atom or the side chain with 3 to 20 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, and the one or more CH wherein in above-mentioned group 2group can by-R 1c=CR 1-,-C ≡ C-, Si (R 1) 2, C=O, C=NR 1,-C (=O) O-,-C (=O) NR 1-, NR 1, P (=O) (R 1) ,-O-,-S-, SO or SO 2replace, or there are 6 to 30 aromatic ring atom and can by one or more R 1the aromatics ring system that group replaces, or not via theheterocyclic nitrogen atom bonding and can by one or more R 1the heteroaromatic ring system with 5 to 30 aromatic ring atom that group replaces, wherein R agroup can with R 1group connects and can form ring;
R bbe selected from H, D and above about R athe group listed, wherein R bgroup can with R 1group connects and can form ring;
R 1be identical or different in each case and be H, D, F, C (=O) R 2, CN, Si (R 2) 3, N (R 2) 2, P (=O) (R 2) 2, OR 2, S (=O) R 2, S (=O) 2r 2, have straight chained alkyl or the alkoxy base of 1 to 20 carbon atom, or have the side chain of 3 to 20 carbon atoms or the alkyl of ring-type or alkoxy base, wherein above-mentioned group can separately by one or more R 2group replaces, and the one or more CH wherein in above-mentioned group 2group can by-R 2c=CR 2-,-C ≡ C-, Si (R 2) 2, C=O, C=NR 2,-C (=O) O-,-C (=O) NR 2-, NR 2, P (=O) (R 2) ,-O-,-S-, SO or SO 2replace, or have aromatics or the heteroaromatic ring system of 5 to 30 aromatic ring atom, each in described ring system can by one or more R 2group replaces, wherein two or more R 1group can be connected to each other and can form ring;
R 2be identical or different in each case and be H, D, F, or have the aliphatic series of 1 to 20 carbon atom, aromatics or heteroaromatic organic radical, wherein one or more hydrogen atoms also can be replaced by D or F; Meanwhile, two or more R 2substituting group can be connected to each other and can form ring;
Its condition is at least one R agroup is selected from F, CF 3, CF 2h, CFH 2, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1with E group, described E group has 6 to 18 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-.
2. compound according to claim 1, is characterized in that described L group is the divalent group being selected from following group: the alkylidene group with 1 to 20 carbon atom, wherein one or more CH 2group can by Si (R 1) 2, O, S, C=O, C=NR 1, C=O-O, C=O-NR 1, NR 1, P (=O) (R 1), SO or SO 2replace and described alkylidene group can by one or more R 1group replaces, or has aromatics or the heteroaromatic ring system of 5 to 30 aromatic ring atom, and each in described ring system can by one or more R 1group replaces; Or for being selected from the trivalent radical of aromatics or the heteroaromatic ring system with 5 to 30 aromatic ring atom, each in described group can by one or more R 1group replaces.
3. compound according to claim 1 and 2, is characterized in that Ar 1be identical or different in each case and be there are 6 to 20 aromatic ring atom and can by one or more R 1the aromatics ring system that group replaces.
4., according to the one or more described compound in claims 1 to 3, it is characterized in that described Y group is identical or different in each case and is singly-bound, C (R 1) 2, NR 1, O or S.
5. according to the one or more described compound in Claims 1-4, it is characterized in that described B group is identical or different in each case and is selected from the group of described formula (A), H, there is the linear alkyl groups of 1 to 10 carbon atom, or there is the side chain of 3 to 10 carbon atoms or the alkyl group of ring-type, each in described group can by one or more R 1group replaces, and has the aromatic yl group of 6 to 14 aromatic ring atom, and each in described group can by one or more R 1group replaces.
6., according to the one or more described compound in claim 1 to 5, it is characterized in that described B group is identical or different in each case and is group or the H of described formula (A).
7., according to the one or more described compound in claim 1 to 6, it is characterized in that described B group is the group of described formula (A).
8., according to the one or more described compound in claim 1 to 7, it is characterized in that described two R agroup is identical or different and is selected from F, CF 3, CN and E group, described E group has 6 to 14 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-, and wherein said heteroaryl groups be not via nitrogen atom bonding.
9., according to the one or more described compound in claim 1 to 8, it is characterized in that R bbe identical or different in each case and be selected from H, F, CF 3, CN, the alkyl group of the linear alkyl groups with 1 to 10 carbon atom or the side chain with 3 to 10 carbon atoms or ring-type, each in described group can by one or more R 1group replaces, and has aryl or the heteroaryl groups of 6 to 14 aromatic ring atom, and each in described group can by one or more R 1group replaces, and wherein said heteroaryl groups is not via nitrogen atom bonding.
10., according to the one or more described compound in claim 1 to 9, it is characterized in that described formula (I) accord with Formula (I-1) is to one of (I-3)
Wherein H, D, there is the alkyl group of 1 to 10 carbon atom or there is aromatics or the heteroaromatic ring system of 6 to 30 aromatic ring atom, wherein each can by one or more R 1group replaces, and is optionally bonded to not planting oneself on the phenyl ring in formula (I-2), and
Wherein said A, R aand R bone or more middle defined in each claim 1 to 9 freely of group, and
Condition is at least one R agroup is selected from F, CF 3, C (=O) R 1, CN, P (=O) (R 1) 2, S (=O) R 1, S (=O) 2r 1with E group, described E group has 6 to 18 aromatic ring atom and can by one or more R 1the aryl that group replaces or heteroaryl groups, and described E group contains the integral part of one or more V group as aromatic ring, wherein said V group be identical or different in each case and be selected from=N-,=C (F)-,=C (CN)-and=C (CF 3)-.
11. 1 kinds of methods prepared according to one or more described formula (I) compound in claim 1 to 10, it is characterized in that being replaced by nucleophilic aromatic or at least one carbazole derivative is introduced in Buchwald coupling, or be characterised in that and introduce at least one electron deficiency heteroaryl groups by Suzuki coupling.
12. 1 kinds containing one or more oligopolymer according to one or more described formula (I) compound in claim 1 to 10, wherein one or more keys forming described oligopolymer can be arranged in formula (I) by R 1or R 2any position replaced.
13. 1 kinds of electron devices, it comprises at least one according to the one or more described compound in claim 1 to 10, or at least one oligopolymer according to claim 12.
14. 1 kinds of organic electroluminescence devices comprising anode, negative electrode and at least one luminescent layer, to is characterized in that in described device that the organic layer that at least one is selected from luminescent layer comprises at least one according to the one or more described compound in claim 1 to 10 or at least one oligopolymer according to claim 12.
15. according to the one or more described compound in claim 1 to 10 or the purposes of oligopolymer according to claim 12 in electron device.
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